Co-deposition of gold nanoparticles and metalloporphyrin using the langmuir-blodgett (LB) technique for Surface-Enhanced Raman Scattering (SERS)

The synergistic effect produced by metallic nanoparticles when incorporated into different systems empowers a research field that is growing rapidly. In addition, organometallic materials are at the center of intensive research with diverse applications such as light-emitting devices, transistors, solar cells, and sensors. The Langmuir-Blodgett (LB) technique has proven to be suitable to address challenges inherent to organic devices, since the film properties can be tuned at the molecular level. Here we report a strategy to incorporate gold nanoparticles (AuNPs) into the LB film by co-deposition in order to achieve surface-enhanced Raman scattering (SERS) of the zinc(II)-protoporphyrin (IX) dimethyl ester (ZnPPIX-DME). Prior to the LB co-deposition, the properties of the Langmuir monolayer of ZnPPIX-DME at the air-water interface, containing AuNPs in the subphase, are studied through the surface-pressure versus mean molecular area (π-A) isotherms. The ZnPPIX-DME+AuNPs π-A isotherm presented a significant shift to higher molecular area, suggesting an interaction between both ZnPPIX-DME molecules and AuNPs. Those interactions are a key factor allowing the co-deposition of both AuNPs and ZnPPIX-DME molecules onto a solid substrate, thus forming the LB film. SERS of ZnPPIX-DME was successfully attained, ensuring the spatial distribution of the AuNPs. Higher enhancement factors were found at AuNP aggregates, as a result of the intense local electromagnetic field found in the metal nanoparticle aggregates. The main vibrational bands observed in the SERS spectra suggest a physical adsorption of the ZnPPIX-DME onto the surface of AuNPs. The latter is not only in agreement with the interactions pointed out by the π-A isotherms but also suggests that this interaction is kept upon LB film co-deposition.

Detecção do peptídeo p17 (HIV) baseado em SERS (Surface-enhanced Raman Spectrosocpy)

Pós-graduação em Química - IQ

Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.

Silver-gold nanotubes containing hot spots on their surface: facile synthesis and surface-enhanced Raman scattering investigations

We report the synthesis of silver-gold nanotubes containing hot spots along their surface. The Ag-Au nanotubes exhibited exceptional SERS properties compared to silver nanowires, enabling the detection of crystal violet in the 10(-10) M regime, as well as 9-nitroanthracene and benzo[a] pyrene at 3.3 x 10(-7) M.

Surface plasmon fluorescence spectroscopy and microscopy studies for biomolecular interaction studies

ABSTARCT Biotechnology has enabled the modification of agricultural materials in a very precise way. Crops have been modified through the insertion of new traits or the inhibition of existing gene functions, named Genetically Modified Organism (GMO), and resulted in improved tolerance of herbicide and/or increased resistance against pests, viruses and fungi. Commercial cultivation of GMO started in 1996 and increased rapidly in 2003 according to a recently released report by the International Service for the Acquisition of Agri-Biotech Applications (ISAAA), depicted continuing consumer resistance in Europe and other part of the world. Upon these developments, the European Union regulations mandated labeling of GMOs containing food and as a consequence, the labeling of GMO containing product in the case of exceeding the1% threshold of alien DNA is required. The aim of the study is to be able to detect and quantify the GMO from the mixture of natural food components. The surface plasmon resonance (SPR) technique combined with fluorescence was used for this purpose. During the presented studies, two key issues are addressed and tried to solve; what is the best strategy to design and built an interfacial architecture of a probe oligonucletide layer either on a two dimensional surface or on an array platform; and what is the best detection method allowing for a sensitive monitoring of the hybridisation events. The study includes two parts: first part includes characterization of different PNAs on a 2D planar surface by defining affinity constants using the very well established optical method “Surface Plasmon Fluorescence Spectroscopy”(SPFS) and on the array platform by “Surface Plasmon Fluorescence Microscopy” (SPFM), and at the end comparison of the sensitivity of these two techniques. The second part is composed of detection of alien DNA in food components by using DNA and PNA catcher probes on the array platform in real-time by SPFM.

Time-resolved surface enhanced resonance Raman spectro-electrochemistry of heme proteins

The membrane protein Cytochrome c Oxidase (CcO) is one of the most important functional bio-molecules. It appears in almost every eukaryotic cell and many bacteria. Although the different species differ in the number of subunits, the functional differences are merely marginal. CcO is the terminal link in the electron transfer pathway of the mitochondrial respiratory chain. Electrons transferred to the catalytic center of the enzyme conduce to the reduction of molecular oxygen to water. Oxygen reduction is coupled to the pumping of protons into the inter-membrane space and hence generates a difference in electrochemical potential of protons across the inner mitochondrial membrane. This potential difference drives the synthesis of adenosine triphosphate (ATP), which is the universal energy carrier within all biological cells. rnrnThe goal of the present work is to contribute to a better understanding of the functional mechanism of CcO by using time-resolved surface enhanced resonance Raman spectroscopy (TR-SERRS). Despite intensive research effort within the last decades, the functional mechanism of CcO is still subject to controversial discussions. It was the primary goal of this dissertation to initiate electron transfer to the redox centers CuA, heme a, heme a3 and CuB electrochemically and to observe the corresponding redox transitions in-situ with a focus on the two heme structures by using SERRS. A measuring cell was developed, which allowed combination of electrochemical excitation with Raman spectroscopy for the purpose of performing the accordant measurements. Cytochrome c was used as a benchmark system to test the new measuring cell and to prove the feasibility of appropriate Raman measurements. In contrast to CcO the heme protein cc contains only a single heme structure. Nevertheless, characteristic Raman bands of the hemes can be observed for both proteins.rnrnIn order to investigate CcO it was immobilized on top of a silver substrate and embedded into an artificial membrane. The catalytic activity of CcO and therefore the complete functional capability of the enzyme within the biomimetic membrane architecture was verified using cyclic voltammetry. Raman spectroscopy was performed using a special nano-structured silver surface, which was developed within the scope of the present work. This new substrate combined two fundamental properties. It facilitated the formation of a protein tethered bilayer lipid membrane (ptBLM) and it allowed obtaining Raman spectra with sufficient high signal-to-noise ratios.rnSpectro-electrochemical investigations showed that at open circuit potential the enzyme exists in a mixed-valence state, with heme a and and heme a3 in the reduced and oxidized state, respectively. This was considered as an intermediate state between the non-activated and the fully activated state of CcO. Time-resolved SERRS measurements revealed that a hampered electron transfer to the redox center heme a3 characterizes this intermediate state.rn

Surface-enhanced vibrational techniques for the detection of synthetic organic colorants

The research project object of this thesis is focused on the development of an advanced analytical system based on the combination of an improved thin layer chromatography (TLC) plate coupled with infrared (FTIR) and Raman microscopies for the detection of synthetic dyes. Indeed, the characterization of organic colorants, which are commonly present in mixtures with other components and in a very limited amount, still represents a challenging task in scientific analyses of cultural heritage materials. The approach provides selective spectral fingerprints for each compound, foreseeing the complementary information obtained by micro ATR-RAIRS-FTIR and SERS-Raman analyses, which can be performed on the same separated spot. In particular, silver iodide (AgI) applied on a gold coated slide is proposed as an efficient stationary phase for the discrimination of complex analyte mixtures, such as dyes present in samples of art-historical interest. The gold-AgI-TLC plate shows high performances related both to the chromatographic separation of analytes and to the spectroscopic detection of components. The use of a mid-IR transparent inorganic salt as the stationary phase avoids interferences of the background absorption in FTIR investigations. Moreover, by ATR microscopy measurements performed on the gold-AgI surface, a considerable enhancement in the intensity of spectra is observed. Complementary information can be obtained by Raman analyses, foreseeing a SERS activity of the AgI substrate. The method has been tested for the characterization of a mixture of three synthetic organic colorants widely used in dyeing processes: Brilliant Green (BG1), Rhodamine B (BV10) and Methylene Blue (BB9).

Redox-Switching in a Viologen-type Adlayer: An Electrochemical Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy Study on Au(111)-(1 x 1) Single Crystal Electrodes

We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1x1) electrode and covered by Au(60 nm)@SlO(2) core shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+),V(+center dot) and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of similar to 3 x 10(5), and up to 9 x 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)- catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces.

Fluorescence-enhanced optical imaging on three-dimensional phantoms using a hand-held probe based frequency-domain intensified charge coupled device (ICCD) optical imager

Fluorescence-enhanced optical imaging is an emerging non-invasive and non-ionizing modality towards breast cancer diagnosis. Various optical imaging systems are currently available, although most of them are limited by bulky instrumentation, or their inability to flexibly image different tissue volumes and shapes. Hand-held based optical imaging systems are a recent development for its improved portability, but are currently limited only to surface mapping. Herein, a novel optical imager, consisting primarily of a hand-held probe and a gain-modulated intensified charge coupled device (ICCD) detector, is developed towards both surface and tomographic breast imaging. The unique features of this hand-held probe based optical imager are its ability to; (i) image large tissue areas (5×10 sq. cm) in a single scan, (ii) reduce overall imaging time using a unique measurement geometry, and (iii) perform tomographic imaging for tumor three-dimensional (3-D) localization. Frequency-domain based experimental phantom studies have been performed on slab geometries (650 ml) under different target depths (1-2.5 cm), target volumes (0.45, 0.23 and 0.10 cc), fluorescence absorption contrast ratios (1:0, 1000:1 to 5:1), and number of targets (up to 3), using Indocyanine Green (ICG) as fluorescence contrast agents. An approximate extended Kalman filter based inverse algorithm has been adapted towards 3-D tomographic reconstructions. Single fluorescence target(s) was reconstructed when located: (i) up to 2.5 cm deep (at 1:0 contrast ratio) and 1.5 cm deep (up to 10:1 contrast ratio) for 0.45 cc-target; and (ii) 1.5 cm deep for target as small as 0.10 cc at 1:0 contrast ratio. In the case of multiple targets, two targets as close as 0.7 cm were tomographically resolved when located 1.5 cm deep. It was observed that performing multi-projection (here dual) based tomographic imaging using a priori target information from surface images, improved the target depth recovery over using single projection based imaging. From a total of 98 experimental phantom studies, the sensitivity and specificity of the imager was estimated as 81-86% and 43-50%, respectively. With 3-D tomographic imaging successfully demonstrated for the first time using a hand-held based optical imager, the clinical translation of this technology is promising upon further experimental validation from in-vitro and in-vivo studies.

Theoretical and numerical investigation of plasmon nanofocusing in metallic tapered rods and grooves

Effective focusing of electromagnetic (EM) energy to nanoscale regions is one of the major challenges in nano-photonics and plasmonics. The strong localization of the optical energy into regions much smaller than allowed by the diffraction limit, also called nanofocusing, offers promising applications in nano-sensor technology, nanofabrication, near-field optics or spectroscopy. One of the most promising solutions to the problem of efficient nanofocusing is related to surface plasmon propagation in metallic structures. Metallic tapered rods, commonly used as probes in near field microscopy and spectroscopy, are of a particular interest. They can provide very strong EM field enhancement at the tip due to surface plasmons (SP’s) propagating towards the tip of the tapered metal rod. A large number of studies have been devoted to the manufacturing process of tapered rods or tapered fibers coated by a metal film. On the other hand, structures such as metallic V-grooves or metal wedges can also provide strong electric field enhancements but manufacturing of these structures is still a challenge. It has been shown, however, that the attainable electric field enhancement at the apex in the V-groove is higher than at the tip of a metal tapered rod when the dissipation level in the metal is strong. Metallic V-grooves also have very promising characteristics as plasmonic waveguides. This thesis will present a thorough theoretical and numerical investigation of nanofocusing during plasmon propagation along a metal tapered rod and into a metallic V-groove. Optimal structural parameters including optimal taper angle, taper length and shape of the taper are determined in order to achieve maximum field enhancement factors at the tip of the nanofocusing structure. An analytical investigation of plasmon nanofocusing by metal tapered rods is carried out by means of the geometric optics approximation (GOA), which is also called adiabatic nanofocusing. However, GOA is applicable only for analysing tapered structures with small taper angles and without considering a terminating tip structure in order to neglect reflections. Rigorous numerical methods are employed for analysing non-adiabatic nanofocusing, by tapered rod and V-grooves with larger taper angles and with a rounded tip. These structures cannot be studied by analytical methods due to the presence of reflected waves from the taper section, the tip and also from (artificial) computational boundaries. A new method is introduced to combine the advantages of GOA and rigorous numerical methods in order to reduce significantly the use of computational resources and yet achieve accurate results for the analysis of large tapered structures, within reasonable calculation time. Detailed comparison between GOA and rigorous numerical methods will be carried out in order to find the critical taper angle of the tapered structures at which GOA is still applicable. It will be demonstrated that optimal taper angles, at which maximum field enhancements occur, coincide with the critical angles, at which GOA is still applicable. It will be shown that the applicability of GOA can be substantially expanded to include structures which could be analysed previously by numerical methods only. The influence of the rounded tip, the taper angle and the role of dissipation onto the plasmon field distribution along the tapered rod and near the tip will be analysed analytically and numerically in detail. It will be demonstrated that electric field enhancement factors of up to ~ 2500 within nanoscale regions are predicted. These are sufficient, for instance, to detect single molecules using surface enhanced Raman spectroscopy (SERS) with the tip of a tapered rod, an approach also known as tip enhanced Raman spectroscopy or TERS. The results obtained in this project will be important for applications for which strong local field enhancement factors are crucial for the performance of devices such as near field microscopes or spectroscopy. The optimal design of nanofocusing structures, at which the delivery of electromagnetic energy to the nanometer region is most efficient, will lead to new applications in near field sensors, near field measuring technology, or generation of nanometer sized energy sources. This includes: applications in tip enhanced Raman spectroscopy (TERS); manipulation of nanoparticles and molecules; efficient coupling of optical energy into and out of plasmonic circuits; second harmonic generation in non-linear optics; or delivery of energy to quantum dots, for instance, for quantum computations.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

SERS substrate for detection of explosives

A novel gold coated femtosecond laser nanostructured sapphire surface – an “optical nose” - based on surface-enhanced Raman spectroscopy (SERS) for detecting vapours of explosive substances was investigated. Four different nitroaromatic vapours at room temperature were tested. Sensor responses were unambiguous and showed response in the range of 0.05 – 15 uM at 25 °C. The laser fabricated substrate nanostructures produced up to an eight-fold increase in Raman signal over that observed on the unstructured portions of the substrate. This work demonstrates a simple sensing system that is compatible with commercial manufacturing practices to detect taggants in explosives which can undertake as part of an integrated security or investigative mission.

Gold nanospikes formed through a simple electrochemical route with high electrocatalytic and surface enhanced Raman scattering activity

We demonstrate a simple electrochemical route to produce uniformly sized gold nanospikes without the need for a capping agent or prior modification of the electrode surface, which are predominantly oriented in the {111} crystal plane and exhibit promising electrocatalytic and SERS properties.

Hybrid polymer/metal nanoparticles with surface enhanced raman tracking for potential use in nanomedicine

This project was a preliminary step towards the development of novel methods for early stage cancer diagnosis and treatment. Diagnostic imaging agents with high Raman signal enhancement were developed based on tailored assemblies of gold nanoparticles, which demonstrated potential for non-invasive detection from deep under the skin surface. Specifically designed polymers were employed to assemble gold nanoparticles into controlled morphologies including dimers, nanochains, nanoplates, globular and core-satellite nanostructures. Our findings suggest that the Raman enhancement is strongly dependent on assembly morphology and can be tuned to adapt to the requirements of the diagnostic agent.